EP0703277A2 - Polyepoxidharze, die Urethane mit Epoxidendgruppen als Zähigkeitsvermittler enthalten - Google Patents

Polyepoxidharze, die Urethane mit Epoxidendgruppen als Zähigkeitsvermittler enthalten Download PDF

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Publication number
EP0703277A2
EP0703277A2 EP95114662A EP95114662A EP0703277A2 EP 0703277 A2 EP0703277 A2 EP 0703277A2 EP 95114662 A EP95114662 A EP 95114662A EP 95114662 A EP95114662 A EP 95114662A EP 0703277 A2 EP0703277 A2 EP 0703277A2
Authority
EP
European Patent Office
Prior art keywords
epoxy resin
epoxy
bisphenol
glycol
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95114662A
Other languages
English (en)
French (fr)
Other versions
EP0703277A3 (de
Inventor
William Edward Starner
Richard Scott Myers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Publication of EP0703277A2 publication Critical patent/EP0703277A2/de
Publication of EP0703277A3 publication Critical patent/EP0703277A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms

Definitions

  • This invention pertains to one part epoxy resin formulations having enhanced fracture toughness.
  • Aromatic polyepoxide resins particularly those based upon the use of polyglycidyl ethers of bisphenol A, have widely been used in applications requiring resistance to high temperature and resistance to chemicals. They have been widely used for preparing electrical laminates for circuit board applications and composites.
  • Heat cured epoxy resins incorporating a heat activated curing agent have been widely used in applications requiring high resistance to chemicals such as electrical lamination and sealants.
  • One of the problems with epoxy resins is their brittleness and attempts have been made to modify these resins through the addition of toughening agents.
  • Toughening agents are based upon the incorporation of aliphatic diepoxides and ester type plasticizers. More recent technology describes incorporation of urethane polymers and carboxy terminated polybutadiene/acrylonitrile copolymers and epoxy adducts of such copolymers.
  • a triglycidyl ether of trihydroxy triphenyl methane is reacted with a polyisocyanate such as toluenediisocyanate, methylene di(phenylisocyanate) and isophoronediisocyanate under conditions such that the isocyanate and epoxy react to form the oxazolidinone structure.
  • a polyisocyanate such as toluenediisocyanate, methylene di(phenylisocyanate) and isophoronediisocyanate
  • US 3,737,406 discloses a process for preparing polyoxazolidones, wherein a polyepoxide is reacted with a polyisocyanate in the presence of chemically reactive epoxy-onium catalyst.
  • the products have a wide range of application such as electrical potting, encapsulant, caulking and adhesive as well as concrete cementing agent.
  • US 4,163,096 discloses epoxy resins having enhanced toughness imparted thereto wherein the epoxy resins are hardened with liquid polymers containing reactive end groups; e.g., butadiene-acrylonitrile polymers having carboxyl end groups.
  • High viscosity is the problem associated with this product.
  • a portion of the glycidyl ether of the polyphenol is reacted with a monoisocyanate, e.g., an aromatic, an aliphatic, cycloaliphatic or aliphatic isocyanate.
  • US 4,742,146 discloses the use of urethane oligomer modified epoxy resins formed by the copolymerization of an epoxy resin and a urethane oligomer containing an oxyalkylene group and polymerizable ethylenically unsaturation in the presence of a catalyst sufficient for effecting oxazolidone formation.
  • the modified epoxy resin compositions can be cured with conventional curing agents and to prepare urethane modified vinyl ester resins.
  • thermoset compositions are suited for fabrication of molded articles and can be combined with conventional reinforcing agents, e.g., glass fiber, aromatic polyamide fiber, etc.
  • US 4,562,227 discloses the production of heat hardenable reaction resin mixtures containing polyfunctional epoxides and polyfunctional isocyanates.
  • One component of the resin reaction mixture is an isocyanate prepolymer formed by reacting a polyisocyanate with a diol where the isocyanate is reacted in a proportion of 0.01 to 0.35 equivalence per diol, and the resulting isocyanate prepolymerizate in a polymethylene polyphenyl isocyanate and an epoxy resin is reacted.
  • Oxazolidone and isocyanate (OX/ICR) formation is effected through the use of an accelerator.
  • US 5,112,932 discloses epoxy terminated polyoxazolidones formed by reacting a polyisocyanate with an epoxide. A combination of oxazolidone rings and isocyanurate rings can be achieved.
  • US 4,719,267 discloses heat curable, one package epoxy resins incorporating polyurethane prepolymers having amine blocked isocyanate groups. Blocked amine curing agents are incorporated into the resin to form sealants.
  • the polyepoxide resins comprise a polyepoxide resin based on a polyglycidyl ether of a phenol, an oxazolidone toughener and a latent curative.
  • the improvement in the polyepoxide resin formulation comprises incorporating an oxazolidone toughener represented by the formula: wherein R is the residue of an aliphatic glycol or aliphatic ether glycol having from 2 to 20 carbon atoms.
  • a recommended formulation for producing the toughened polyepoxide resin is as follows:
  • the polyepoxide resins useful for practicing the present invention are those polyglycidyl ethers of phenolic type compounds having terminal 1,2-epoxy groups.
  • the epoxide equivalents of these glycidyl ethers is greater than one and the equivalent weight ranges from 150 to 10000 preferably 150 to 1500.
  • Polyglycidylethers of bisphenol A are particularly suited as polyepoxides for the production of composities and electrical circuit boards and the resin includes polyglycidyl ethers of phenol/formaldehyde and diphenol/formaldehyde novolacs as well as the polyglycidyl ethers of tri(hydroxyphenyl)methane and tetra(hydroxyphenyl)ethanes and propanes.
  • Epoxy-terminated urethane prepolymers incorporating the oxazolidone structure comprise the reaction product of an isocyanate-terminated urethane prepolymer and a polyepoxide.
  • Isocyanate-terminated prepolymers are prepared by reacting a polyfunctional isocyanate, typically an aromatic diisocyanate, with a polyol, preferably a long chain polyether or polyester polyol, such as ethylene and propyleneoxide adducts of C2 to C4 polyols.
  • the molecular weight (mw) of the polyol should range from about 1000 to 8000, preferably from about 3000 to 4000.
  • the preferred polyisocyanate prepolymer can be prepared by any known means, for example, a 2000 mw polypropylene glycol can be reacted with an 80/20 2,4/2,6-toluenediisocyanate mixture to produce the isocyanate terminated prepolymer.
  • Any polyisocyanate such as methylenedi(phenyldiisocyanate) (MDI), isophoronediisocyanate (IPDI) or para -phenylenediisocyanate (PPDI) is also suitable.
  • the epoxy terminated urethane prepolymers then are prepared by reacting the isocyanate-reactive prepolymers with a polyepoxide resin under conditions for forming the epoxy terminated urethanes incorporating the oxazolidone structure.
  • a catalyst e.g., potassium acetate at temperatures of from 120 to 190°C. In the absence of a catalyst, the oxazolidone structure may not be obtained.
  • the latent curative for forming the cured polyepoxide resin product include dicyandiamide and the like.
  • Dicyandiamide is the preferred latent amine and it can be used with other amines, e.g., aromatic diamines like methylenedianiline and hydrogenated derivatives, isophoronediamine, and the like. Generally, any aromatic or alicyclic diamine or latent amine curative used as an epoxy curative for heat cured applications may be utilized.
  • the resulting epoxy terminated polyurethane, as tougheners, have viscosities in the 400-600 poises range, whereas commercial tougheners based upon carboxyl terminated butadiene/acrylonitrile copolymers have viscosities in the range of 3000-8000 poises. Lower viscosities are easier to accommodate in industrial equipment.
  • the physical properties and particularly the degree of toughness is generally dependent upon the ratio of toughener and amine and bisphenol A resin.
  • a polyisocyanate prepolymer was first prepared by reacting 107g of 80/20 TDI (0.61 moles) and 875g of 3000 Mw polypropylene glycol (PPG) (0.29 moles). The materials were mixed together and heated to 80°C with agitation under a nitrogen blanket. The temperature was held between 80 and 90°C for 8-10 hours with agitation.
  • PPG polypropylene glycol
  • the ETU was then prepared by adding 2048g of bisphenol A diglycidyl ether (Epon 828) and 0.8g of anhydrous potassium acetate and heating the resulting mixture to 160°C. After 1 hour at 160°C, all traces of isocyanate were gone according to IR measurements. A 99% recovery (3000g) was obtained.
  • the ETU concentration was 40% with an epoxy equivalent weight of 300 and a viscosity of 560 poise.
  • a polyisocyanate prepolymer was prepared by reacting 182.7g of 80/20 TDI (1.05 moles) and 1000g of 2000 Mw PPG (0.5 moles). The materials were mixed together and heated to 80°C with agitation under a nitrogen blanket. The temperature was held between 80 and 90°C for 8-10 hours with agitation.
  • the ETU was then prepared by adding 2713g of bisphenol A diglycidyl ether (Epon 828) and 0.8g of anhydrous potassium acetate and heating the resulting mixture to 160°C. After 1 hour at 160°C, all traces of isocyanate were gone according to IR measurements. A 99% recovery (3895g) was obtained.
  • the ETU concentration was 40% with an epoxy equivalent weight of 290 and a viscosity of 600 poise.
  • a polyisocyanate prepolymer was prepared by reacting 91 g of 80/20 TDI (0.525 moles) and 1000 g of 4000 Mw PPG (0.25 moles). The materials were mixed together and heated to 80°C with agitation under a nitrogen blanket. The temperature was held between 80 and 90°C for 8-10 hr with agitation. The ETU was then prepared by adding 2130 g of bisphenol A diglycidyl ether (Epon 828) and 0.8 g of anhydrous potassium acetate and heating the resulting mixture to 160°C. After 1 hr at 160°C all traces of isocyanate were gone according to IR measurements. A 99% recovery (3188 g) was obtained. The ETU concentration was 40% with an epoxy equivalent weight of 300 and a viscosity of 500 poise.
  • the formulations in this study were comprised of 37.5 phr toughening additive containing 40% active toughener, 6 phr dicyandiamide (DICY) and 2 phr Amicure UR catalyst using Epon 828 epoxy resin.
  • the test specimens were cured at 140°C for 1 hr. Table 1 sets forth the results.
  • Table 1 shows the properties of a cured one part epoxy formulation containing no toughener.
  • Column 2 shows the effect of Epi-Rez 58005 (a commercial adduct of a carboxy terminated butadiene-acrylonitrile and Bisphenol A epoxy resins dissolved in excess resin).
  • Columns 3, 4 & 5 show the effect of ETUs prepared from various molecular weight polypropylene glycols. The best properties were obtained with the ETU prepared from a 3000 Mw PPG.
  • the 3000 ETU In addition to improving the fracture toughness and adhesive properties, the 3000 ETU also has a positive impact on the glass transition temperature (Tg).
  • Tg glass transition temperature
  • the Tg of the 3000 ETU formulation is higher than both the non-toughened formulation and the formulation toughened with Epi-Rez 58005.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP95114662A 1994-09-21 1995-09-18 Polyepoxidharze, die Urethane mit Epoxidendgruppen als Zähigkeitsvermittler enthalten Withdrawn EP0703277A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US309712 1994-09-21
US08/309,712 US5480958A (en) 1994-09-21 1994-09-21 Polyepoxide resins incorporating epoxy terminated urethanes as tougheners

Publications (2)

Publication Number Publication Date
EP0703277A2 true EP0703277A2 (de) 1996-03-27
EP0703277A3 EP0703277A3 (de) 1996-07-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP95114662A Withdrawn EP0703277A3 (de) 1994-09-21 1995-09-18 Polyepoxidharze, die Urethane mit Epoxidendgruppen als Zähigkeitsvermittler enthalten

Country Status (3)

Country Link
US (1) US5480958A (de)
EP (1) EP0703277A3 (de)
JP (1) JP2785181B2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062924A (zh) * 2020-08-21 2020-12-11 南京聚发新材料有限公司 缠绕工艺用聚氨酯树脂、树脂/纤维复合材料及其制备方法和应用

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998044017A1 (fr) * 1997-03-27 1998-10-08 Mitsubishi Rayon Co., Ltd. Composition de resine epoxyde pour plastique renforce de fibre de verre, preimpregne et moulage tubulaire produit au moyen de cette composition
GB9817799D0 (en) * 1998-08-14 1998-10-14 Dow Deutschland Inc Viscosity modifier for thermosetting resin compositioning
JP4687224B2 (ja) * 2004-04-23 2011-05-25 東レ株式会社 エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
JP2008081686A (ja) * 2006-09-28 2008-04-10 Sumitomo Bakelite Co Ltd 液状エポキシ樹脂組成物およびそれを用いた半導体装置
FR2951876B1 (fr) * 2009-10-26 2012-02-03 Commissariat Energie Atomique Micro-batterie au lithium munie d'une couche d'encapsulation conductrice electroniquement
PT2606079E (pt) 2010-08-16 2014-10-08 Bayer Ip Gmbh Componente compósito reforçado com fibras e um processo para a sua produção
CN103649154A (zh) * 2011-07-04 2014-03-19 陶氏环球技术有限责任公司 在可热固化的环氧树脂体系中作为增韧剂的加合物
US9714361B2 (en) 2013-03-15 2017-07-25 Lake Region Manfacturing, Inc. Oxirane (ethylene oxide) polyurethane coatings
US9255173B2 (en) * 2013-03-15 2016-02-09 Lake Region Manufacturing, Inc. Oxirane (ethylene oxide) polyurethane coatings
BR112016002599A2 (pt) * 2013-08-16 2017-08-01 Dow Global Technologies Llc composição de epóxi termofixa 1k
EP3143059B1 (de) * 2014-05-12 2018-01-10 Covestro Deutschland AG Katalysatoren für die synthese von oxazolidinonverbindungen
JP6766323B2 (ja) * 2015-06-05 2020-10-14 Dic株式会社 ポリウレタン変性エポキシ樹脂及び接着剤
KR20180066107A (ko) * 2015-10-13 2018-06-18 다우 글로벌 테크놀로지스 엘엘씨 고처리량 제조 공정에서 사용하기 위한 속경화 에폭시 조성물
KR102183907B1 (ko) * 2016-12-28 2020-11-27 주식회사 엘지화학 열가소성 난연 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품
US11332609B2 (en) * 2017-06-29 2022-05-17 Dow Global Technologies Llc Epoxy-fiber reinforced composites, method to form the composites and epoxy resin composition used therefor
WO2019116181A1 (en) 2017-12-12 2019-06-20 3M Innovative Properties Company Compositions including alpha-alumina particles and methods of their use
US12570870B2 (en) 2019-04-11 2026-03-10 3M Innovative Properties Company Curable compositions, abrasion-resistant articles, and method of thermoforming the same
CN116162327A (zh) * 2021-11-24 2023-05-26 南通星辰合成材料有限公司 一种湿法缠绕用环氧树脂材料及其制备方法
EP4543955A1 (de) * 2022-06-22 2025-04-30 Basf Se Epoxy-terminierte isocyanat-prepolymere und verfahren zu deren herstellung
CN116218147A (zh) * 2022-12-22 2023-06-06 四川东树新材料有限公司 一种低放热的改性环氧树脂组合物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3737406A (en) 1971-03-22 1973-06-05 Alelio G D Reactive epoxy-onium catalysts for synthesis of polyoxazolidones
US3876618A (en) 1971-08-19 1975-04-08 Dow Chemical Co Oxazolidinone modified triglycidyl ether of trihydroxy triphenyl methane and derivatives thereof
US4163096A (en) 1977-11-02 1979-07-31 Ciba-Geigy Corporation Epoxy resin mixture for the production of flexible moulded articles
US4424316A (en) 1981-10-08 1984-01-03 Stauffer Chemical Company Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom
US4562227A (en) 1983-06-27 1985-12-31 Siemens Aktiengesellschaft Heat-hardenable reaction resin mixtures comprising polyfunctional epoxide, polyisocyanate prepolymer and a reaction accelerator which is either a tertiary amine or an imidazole
US4719267A (en) 1984-02-16 1988-01-12 Essex Specialty Products, Inc. Heat curable one package polyurethane resin composition
US4742146A (en) 1985-10-18 1988-05-03 The Dow Chemical Company Urethane modified epoxy resin compositions containing oxazolidinone or thiazolidinone groups
US5112932A (en) 1989-06-06 1992-05-12 The Dow Chemical Company Epoxy-terminated polyoxazolidones and process for the preparation thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3413377A (en) * 1965-12-21 1968-11-26 Baker Chem Co J T Resins of poly(epoxyalkyl-2-oxazolidinone), phenolic based polyepoxides and monoepoxy compounds
US3694406A (en) * 1970-07-31 1972-09-26 Us Air Force Preparation of polyoxazolidones
JPS56127676A (en) * 1980-03-12 1981-10-06 Asahi Denka Kogyo Kk Adhesive composition
JPS59204611A (ja) * 1983-04-30 1984-11-20 ダブリユ・ア−ル・グレイス　アンド　カンパニ− 熱可塑性，エポキシ懸垂，ウレタン含有化合物
JP2829814B2 (ja) * 1993-05-17 1998-12-02 日本ペイント株式会社 ソフトセグメントを含んでいる電着用変性エポキシ樹脂

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3737406A (en) 1971-03-22 1973-06-05 Alelio G D Reactive epoxy-onium catalysts for synthesis of polyoxazolidones
US3876618A (en) 1971-08-19 1975-04-08 Dow Chemical Co Oxazolidinone modified triglycidyl ether of trihydroxy triphenyl methane and derivatives thereof
US4163096A (en) 1977-11-02 1979-07-31 Ciba-Geigy Corporation Epoxy resin mixture for the production of flexible moulded articles
US4424316A (en) 1981-10-08 1984-01-03 Stauffer Chemical Company Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom
US4562227A (en) 1983-06-27 1985-12-31 Siemens Aktiengesellschaft Heat-hardenable reaction resin mixtures comprising polyfunctional epoxide, polyisocyanate prepolymer and a reaction accelerator which is either a tertiary amine or an imidazole
US4719267A (en) 1984-02-16 1988-01-12 Essex Specialty Products, Inc. Heat curable one package polyurethane resin composition
US4742146A (en) 1985-10-18 1988-05-03 The Dow Chemical Company Urethane modified epoxy resin compositions containing oxazolidinone or thiazolidinone groups
US5112932A (en) 1989-06-06 1992-05-12 The Dow Chemical Company Epoxy-terminated polyoxazolidones and process for the preparation thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062924A (zh) * 2020-08-21 2020-12-11 南京聚发新材料有限公司 缠绕工艺用聚氨酯树脂、树脂/纤维复合材料及其制备方法和应用

Also Published As

Publication number Publication date
JPH08109245A (ja) 1996-04-30
EP0703277A3 (de) 1996-07-31
JP2785181B2 (ja) 1998-08-13
US5480958A (en) 1996-01-02

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